[1] He made his debut in the television series Black & White (2009), for which he won the Golden Bell Award for Best Actor.

After collaborating with director Doze Niu in Monga (2010) and Love (2012), he shifted his career to China, starring in films Caught in the Web (2012), So Young (2013), Young Detective Dee: Rise of the Sea Dragon (2013), Chronicles of the Ghostly Tribe (2015), Her Story (2024) as well as the television series Eternal Love (2017).

[12] Chao then starred in Zhao Wei's directorial debut So Young (2013), playing an ambitious and nerdy China university student.

The film, directed by Lu Chuan, was a hit at the box office but received mixed reviews in regard to its faithfulness to the novel.

[20] Though Chao's casting as the beautiful male lead was originally met with criticism, he eventually won praise for his acting.

They did not acknowledge their relationship until 2014, when they promoted their film Black & White: The Dawn of Justice on TV talkshow Kangsi Coming.

The two met on the set of Caught in the Web[27] and welcomed a daughter, Rhea Chao, in June 2019, one month after announcing that Gao was pregnant.